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Title: Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation

Abstract

Pulse radiolysis has been used to investigate intramolecular electron transfer in a series of molecules in which dimethoxynapththalene (M/sub 2/N) and dicyanovinyl (DCV) groups are held at fixed distance and orientation by rigid saturated hydrocarbon bridges. Electron transfer from M/sub 2/N/sup -/ to DCV is faster than 1 x 10/sup 9/ s/sup -1/ for compounds in which the two groups are separated by 4, 6, 8, 10, or 12 saturated carbon-carbon bonds. For the 4-, 6-, and 8-bond compounds, optical electron transfer bands are present in the visible - near-infrared absorption spectra of the anions. The positions shift to higher energies with increasing solvent polarity. Their intensities are large (epsilon approx. = 2000 M/sup -1/ cm/sup -1/ for the 4-bond compound) and decrease rapidly as the length of the bridge increases. It is clear that exceptionally large, long-distance electronic coupling of the two ..pi.. systems occurs through the saturated bonds of the bridge. These electronic couplings are 0.16, 0.06, and 0.03 eV across 4-, 6-, and 8-bond bridges. Even larger couplings have been observed previously by photoelectron spectroscopy, but not for such large ..pi.. systems. With these large electronic couplings, long-distance electron transfer in the 4- and 6-bond compounds ismore » expected to be adiabatic. Even for the 8-bond compound with a center-to-center distance of approx.12 A the electron-transfer rate reduced from the optical electron-transfer absorption band is > 10/sup 12/ s/sup -1/.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab., IL
OSTI Identifier:
6089560
DOE Contract Number:  
W-31-109-ENG-38
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:17
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; CONDENSED AROMATICS; ELECTRON TRANSFER; RADIOLYSIS; CYANIDES; ORGANIC OXYGEN COMPOUNDS; VINYL MONOMERS; CHEMICAL BONDS; EXPERIMENTAL DATA; AROMATICS; CHEMICAL RADIATION EFFECTS; CHEMICAL REACTIONS; CHEMISTRY; DATA; DECOMPOSITION; INFORMATION; MONOMERS; NUMERICAL DATA; ORGANIC COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; 400600* - Radiation Chemistry

Citation Formats

Penfield, K W, Miller, J R, Paddon-Row, M N, Cotsaris, E, Oliver, A M, and Hush, N S. Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation. United States: N. p., 1987. Web. doi:10.1021/ja00251a001.
Penfield, K W, Miller, J R, Paddon-Row, M N, Cotsaris, E, Oliver, A M, & Hush, N S. Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation. United States. https://doi.org/10.1021/ja00251a001
Penfield, K W, Miller, J R, Paddon-Row, M N, Cotsaris, E, Oliver, A M, and Hush, N S. 1987. "Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation". United States. https://doi.org/10.1021/ja00251a001.
@article{osti_6089560,
title = {Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation},
author = {Penfield, K W and Miller, J R and Paddon-Row, M N and Cotsaris, E and Oliver, A M and Hush, N S},
abstractNote = {Pulse radiolysis has been used to investigate intramolecular electron transfer in a series of molecules in which dimethoxynapththalene (M/sub 2/N) and dicyanovinyl (DCV) groups are held at fixed distance and orientation by rigid saturated hydrocarbon bridges. Electron transfer from M/sub 2/N/sup -/ to DCV is faster than 1 x 10/sup 9/ s/sup -1/ for compounds in which the two groups are separated by 4, 6, 8, 10, or 12 saturated carbon-carbon bonds. For the 4-, 6-, and 8-bond compounds, optical electron transfer bands are present in the visible - near-infrared absorption spectra of the anions. The positions shift to higher energies with increasing solvent polarity. Their intensities are large (epsilon approx. = 2000 M/sup -1/ cm/sup -1/ for the 4-bond compound) and decrease rapidly as the length of the bridge increases. It is clear that exceptionally large, long-distance electronic coupling of the two ..pi.. systems occurs through the saturated bonds of the bridge. These electronic couplings are 0.16, 0.06, and 0.03 eV across 4-, 6-, and 8-bond bridges. Even larger couplings have been observed previously by photoelectron spectroscopy, but not for such large ..pi.. systems. With these large electronic couplings, long-distance electron transfer in the 4- and 6-bond compounds is expected to be adiabatic. Even for the 8-bond compound with a center-to-center distance of approx.12 A the electron-transfer rate reduced from the optical electron-transfer absorption band is > 10/sup 12/ s/sup -1/.},
doi = {10.1021/ja00251a001},
url = {https://www.osti.gov/biblio/6089560}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:17,
place = {United States},
year = {Wed Aug 19 00:00:00 EDT 1987},
month = {Wed Aug 19 00:00:00 EDT 1987}
}